Syntheses, crystal structures, optical and theoretical studies of the actinide thiophosphates SrU(PS4)2, BaU(PS4)2, and SrTh(PS4)2

Adel Mesbah; Jai Prakash; Jessica C. Beard; Sébastien Lebègue; Christos D. Malliakas; James A. Ibers

doi:10.1021/acs.inorgchem.5b00071

Syntheses, crystal structures, optical and theoretical studies of the actinide thiophosphates SrU(PS₄)₂, BaU(PS₄)₂, and SrTh(PS₄)₂

Adel Mesbah, Jai Prakash, Jessica C. Beard, Sébastien Lebègue, Christos D. Malliakas, James A. Ibers^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

11 Scopus citations

Abstract

Three new actinide thiophosphates, SrU(PS₄)₂, BaU(PS₄)₂, and SrTh(PS₄)₂, have been synthesized by high-temperature solid-state methods, and their crystal structures were determined from single-crystal X-ray diffraction studies. These three isostructural compounds crystallize in a new structure type in space group D_4h13-P4₂/mbc of the tetragonal system. Their structure features infinite one-dimensional chains of ∞1[An(PS₄)₂^2-] anions (An = U or Th). Each An atom is coordinated by eight S atoms in a bicapped trigonal prism, and each P atom is tetrahedrally bonded to four S atoms. The compounds are readily charge balanced as Ak²⁺An⁴⁺(P⁵⁺(S^2-)₄)₂. Optical studies on single crystals of SrU(PS₄)₂ and BaU(PS₄)₂ as well as ground single crystals of SrTh(PS₄)₂ revealed a direct band gap of 2.13(2) eV and an indirect band gap value of 1.99(2) eV for SrU(PS₄)₂ and a direct and indirect gap of about 2.28(2) eV for BaU(PS₄)₂. SrTh(PS₄)₂ has a relatively large band gap of 3.02(2) eV. DFT calculations for SrU(PS₄)₂ and BaU(PS₄)₂ using the HSE functional predict both compounds to be antiferromagnetic and have very similar electronic structures with band gaps of 2.7 eV. The band gap calculated for SrTh(PS₄)₂ is 3.2 eV.

Original language	English (US)
Pages (from-to)	2970-2975
Number of pages	6
Journal	Inorganic chemistry
Volume	54
Issue number	6
DOIs	https://doi.org/10.1021/acs.inorgchem.5b00071
State	Published - Mar 16 2015

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Physical and Theoretical Chemistry
Inorganic Chemistry

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title = "Syntheses, crystal structures, optical and theoretical studies of the actinide thiophosphates SrU(PS4)2, BaU(PS4)2, and SrTh(PS4)2",

abstract = "Three new actinide thiophosphates, SrU(PS4)2, BaU(PS4)2, and SrTh(PS4)2, have been synthesized by high-temperature solid-state methods, and their crystal structures were determined from single-crystal X-ray diffraction studies. These three isostructural compounds crystallize in a new structure type in space group D4h13-P42/mbc of the tetragonal system. Their structure features infinite one-dimensional chains of ∞1[An(PS4)22-] anions (An = U or Th). Each An atom is coordinated by eight S atoms in a bicapped trigonal prism, and each P atom is tetrahedrally bonded to four S atoms. The compounds are readily charge balanced as Ak2+An4+(P5+(S2-)4)2. Optical studies on single crystals of SrU(PS4)2 and BaU(PS4)2 as well as ground single crystals of SrTh(PS4)2 revealed a direct band gap of 2.13(2) eV and an indirect band gap value of 1.99(2) eV for SrU(PS4)2 and a direct and indirect gap of about 2.28(2) eV for BaU(PS4)2. SrTh(PS4)2 has a relatively large band gap of 3.02(2) eV. DFT calculations for SrU(PS4)2 and BaU(PS4)2 using the HSE functional predict both compounds to be antiferromagnetic and have very similar electronic structures with band gaps of 2.7 eV. The band gap calculated for SrTh(PS4)2 is 3.2 eV.",

author = "Adel Mesbah and Jai Prakash and Beard, {Jessica C.} and S{\'e}bastien Leb{\`e}gue and Malliakas, {Christos D.} and Ibers, {James A.}",

note = "Publisher Copyright: {\textcopyright} 2015 American Chemical Society.",

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doi = "10.1021/acs.inorgchem.5b00071",

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T1 - Syntheses, crystal structures, optical and theoretical studies of the actinide thiophosphates SrU(PS4)2, BaU(PS4)2, and SrTh(PS4)2

AU - Mesbah, Adel

AU - Prakash, Jai

AU - Beard, Jessica C.

AU - Lebègue, Sébastien

AU - Malliakas, Christos D.

AU - Ibers, James A.

PY - 2015/3/16

Y1 - 2015/3/16

N2 - Three new actinide thiophosphates, SrU(PS4)2, BaU(PS4)2, and SrTh(PS4)2, have been synthesized by high-temperature solid-state methods, and their crystal structures were determined from single-crystal X-ray diffraction studies. These three isostructural compounds crystallize in a new structure type in space group D4h13-P42/mbc of the tetragonal system. Their structure features infinite one-dimensional chains of ∞1[An(PS4)22-] anions (An = U or Th). Each An atom is coordinated by eight S atoms in a bicapped trigonal prism, and each P atom is tetrahedrally bonded to four S atoms. The compounds are readily charge balanced as Ak2+An4+(P5+(S2-)4)2. Optical studies on single crystals of SrU(PS4)2 and BaU(PS4)2 as well as ground single crystals of SrTh(PS4)2 revealed a direct band gap of 2.13(2) eV and an indirect band gap value of 1.99(2) eV for SrU(PS4)2 and a direct and indirect gap of about 2.28(2) eV for BaU(PS4)2. SrTh(PS4)2 has a relatively large band gap of 3.02(2) eV. DFT calculations for SrU(PS4)2 and BaU(PS4)2 using the HSE functional predict both compounds to be antiferromagnetic and have very similar electronic structures with band gaps of 2.7 eV. The band gap calculated for SrTh(PS4)2 is 3.2 eV.

AB - Three new actinide thiophosphates, SrU(PS4)2, BaU(PS4)2, and SrTh(PS4)2, have been synthesized by high-temperature solid-state methods, and their crystal structures were determined from single-crystal X-ray diffraction studies. These three isostructural compounds crystallize in a new structure type in space group D4h13-P42/mbc of the tetragonal system. Their structure features infinite one-dimensional chains of ∞1[An(PS4)22-] anions (An = U or Th). Each An atom is coordinated by eight S atoms in a bicapped trigonal prism, and each P atom is tetrahedrally bonded to four S atoms. The compounds are readily charge balanced as Ak2+An4+(P5+(S2-)4)2. Optical studies on single crystals of SrU(PS4)2 and BaU(PS4)2 as well as ground single crystals of SrTh(PS4)2 revealed a direct band gap of 2.13(2) eV and an indirect band gap value of 1.99(2) eV for SrU(PS4)2 and a direct and indirect gap of about 2.28(2) eV for BaU(PS4)2. SrTh(PS4)2 has a relatively large band gap of 3.02(2) eV. DFT calculations for SrU(PS4)2 and BaU(PS4)2 using the HSE functional predict both compounds to be antiferromagnetic and have very similar electronic structures with band gaps of 2.7 eV. The band gap calculated for SrTh(PS4)2 is 3.2 eV.

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SN - 0020-1669

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SP - 2970

EP - 2975

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 6

ER -

Syntheses, crystal structures, optical and theoretical studies of the actinide thiophosphates SrU(PS₄)₂, BaU(PS₄)₂, and SrTh(PS₄)₂

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